Azo dyestuffs derived from 2.3-hydroxynaphthoyl-2-amino-3-naphtholethers



30 with a diazosolution 40 ther advantage that the 50 bath.

' Patented Aug. 20, 1929 UNITED STATES PATENT OFFICE.

LEOPOLD LASKA AND ARTHUR ZITSCHER, OF OFFENBACH-ON-THE-MAIN, GERMANY,ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORA-TION OF DELAWARE.

AZO DYESTUFFS DERIVED FROM 2.3--HYDROXYNAPHTEOYL-2-AMINO-3-NAPE-THOLETHEBS.

N Drawing. Application filed December 16, 1927, Serial No. 240,634, andin Germany December 31., 1926.

Our invention relates to new azodyestufls corresponding to the generalformula O O NH O-alkyl which are when dry reddish to blackish powders,soluble in concentrated sulfuric acid with a reddish-violet to greencolor, suitable for the production of valuable color lakes and yieldingwhen produced on the vegetable fiber dyeings distinguished by aremarkable fastness to rubbing.

v The new dyestuffs are obtainable by combining a diazo-, tetrazoordiazoazocompound 2.3- ydroxynaphthoyl -2- amino 3 -naphtholethers beingdistin uished by a special afiinity to the vegetable fiber and a verygood solubility. It is therefore possible to treat the padded dye-goodprior to the develo ment with a rinsing so utio'n whereby an excellentfastness to rubbing of the dyed material is provided. The abovementioned good solubility of the2.3-hydroxynaphthoyl-2-amino-3-naphtholethers enables the dyer to usestrongly concentrated stocksolutions for dyeing in the standing bath,which process is an absolute commercial necessit- The 2.3-hydroxynaphthol-2-amino- 3-nap tholethers are distinguishe by the furadding liquordoes not need an addition 0 formaldehyde, the hanks, which areimpregnated with the 2.3- hydrox naphthoyl 2 amino 3 naphtholethers,being resistant to the air without this 4.") addition. In consequencethereof the stocksolutions are stable without any limit. All theseadvantages make the 2.3-hydroxynaphthoyl-2-amino-3-naphtholethersespecially suitable for the dyeing process in a standing They areunknown hitherto and may be prepared for instance according to theprocess described in U. S. Patent No. 1,101,111. The2.3-hydroxynaphthoyl 2 amino 3 naphthol- Inethylether crystallizes fromtoluene in the form of feebly colored needles, melting at l97198.

In order to further illustrate our invention the following examples aregiven the parts being by weight and all temperatures in centigradedegrees. But we wish it to be understood that we are not limited to theparticular conditions nor specific products mentioned therein.

Emample 1.A diazosolution prepared in the usual manner from 17,5 partsof 4-nitro- 2-amino-1-anisole, is combined with a solution in dilutecaustic soda solution of 25 parts of 2.3-hydroxynaphthoyl-2-amino-3-naphtholmethylether, containing a sufficient amount of SOdllll'l'lacetate for-neutralizing the excess of mineral acid. The separateddyestuflI' corresponding probably to the formula:

C0-NH o cm is filtered off and well washed. It dissolves in concentratedsulfuric acid with a reddishviolet color. It may be advantageously usedin form of a aste and yields,'when mixed with the usuai substrate, abluish redcolor lake of a good fastncss.

In order'to produce the dyestufi' on the fiber one may proceed asfollows:

Well boiled and dried cotton yarn is handled for about half-an-hour in asolution, containing 2,5 grs of 2.3-hydroxynaphthoyl-2-amino-3-naphtholmethylether, 6 cc. of a caustic soda solution of 34B6. and 5 cc. of Turkey red oil in the liter, well wrung out andcentrifugated. It is developed with a diazosolution containing 1,75 grs.of -nitro- 1.2-anisidine in the liter and being neutralized with sodiumacetate, rinsed, soa-ped and a Turkey red .shade isobtained.

Ewample 2.-For dyeing in a standing bath 200 grs. of2-3-hydroxynaphthoyl-2-amino- 3-naphtholmethylether, 500 cc. of acaustic soda solution of 34 B., and 400 cc. of Turkey red oil aredissovled to 10 liters of, a stocksolution.

For one dyeing-operation 1 part of this stock-solution is diluted with7. parts of water and the dye-good is padded as described inexample 1the proportion of material to be dyed to the liquor being 1:20. Whendeveloping in the usual manner with a diazosolution of5-chloro-2-amino-l-toluene, which is additioned of a basic aluminiumsulfate solution for neutralizing the excess of mineral acid, a clearbluish reddyeing of a very good fastness to kier boiling is ob taine Forfurther lots the bath is replenished with 1 liter of the aforesaid stocksolution pro 1 kg. of dry material.

The padding operation may be carried out in the same mannerwith additionof formaldehyde.

In the following table the shades of some further dyestuffs, produced onthe fiber, are given:

2.3-hydroxynaphthoyl-2.3-aminonaphtholmethyletheryields, when developedwith the diazocompound of Shade. 4-amino-1.3-dimethy1benzene Full red.4-chloroanlllnc Yellowish scarlet.

5-bromo2-amlno-Lmethylbenzene--. Bluish red. 2 amlnO-E-chlorophenyI-fl-naphthylether Clear red. 4-amlno-3-chloro-benzanillde Yellowish red.2.5-dichloroanlline Yellowish red. 2.5-d1bromoaniline Yellowisli red. 2amino 5.2'.5' trichlorodiphenylether. Clear red. 2.3-dichloroanllineReddish orange. 2.3.4-trichloroaniline Yellowlsh red.3-nltro-4-amino-1-methylbenzene Claret red. 2-chloro-5-nitro-anilineYellowish rcd. 5-chlor0-2-nitroanillne- .Yellowish red. 3-amlno-4-nltro-6-methoxy-1-methy1- benzene Bluish garnet.o-amlnoazotoluene Garnet. 4-amlno-2.5'-(llchloro-5.2'-dimcthoxyazobenzene Dark violet. 4'-nltro-4-aminoazobcnzene .J Bluish ruet.1.5-diamlnoanthraquinone Clear v olet.2.3-hydroxynaghthoyl-2.3-amlnonaphtholethylether yields, when developedwith the dlazocompound of 2-chloro-4-nltroaniline Yellowish red.5-nitro-2-amino-1-metl1y1benzene Red. l-amlno-anthraquinone Yellowlshred.

- the process may be effected in the same man- 1. As new compoundsazodye'stuifs, corresponding probably to the general formula:

stufi's which process comprises combining any aromatic diazocompoundwith a 2.3-hydroxynaphthoyl-Q-amino-3-naphtholether.

3. Textile material dyed with the dyestufl's as claimed in claim 1, saiddyestuffs being produced on the vegetable fiber.

4. As new compounds azodyestufi's, corresponding probably to the generalformula:

oo-NH N-'N-o Halogen which are when dry reddish powders, soluble inconcentrated sulfuric acid with a reddish violet to green color, beingsuitable for the production of valuable color lakes and yielding w-henproduced on the vegetable fiber red dyeings o a'remarkable fastness torubbin 8. Textile material dyed with the dyestui s as claimed in claim7, said dyestuffs being produced on the vegetable fiber.

9. As new compound azodyestufis corresponding to the probable formula:

1 THalogen stufi's as claimed in claim 9, said dyestufis being producedon the vegetable fiber.

s a new compound the azodyestufi' probable formula:

11. A corresponding to the which is when dry a reddish powder, solublein concentrated sulfuric acid with a reddish violet color, beingsuitable for the production of valuable color lakesand ielding whenproduced on the vegetable filzer bluish red dyeings of a remarkablefastness to rubbing.

12. Textile material dyedwith the dyestufi as claimed in claim 11, saiddyestufi being produced on the vegetable fiber.

'In testimony whereof, we alfix our signatures.

LEOPOLD LASKA. ARTHUR ZITSCHER.

